CN105731861B - Surface of graphene oxide molecular imprinting composite material and preparation method thereof for tracking poly carboxylic acid series water reducer - Google Patents
Surface of graphene oxide molecular imprinting composite material and preparation method thereof for tracking poly carboxylic acid series water reducer Download PDFInfo
- Publication number
- CN105731861B CN105731861B CN201610092458.3A CN201610092458A CN105731861B CN 105731861 B CN105731861 B CN 105731861B CN 201610092458 A CN201610092458 A CN 201610092458A CN 105731861 B CN105731861 B CN 105731861B
- Authority
- CN
- China
- Prior art keywords
- parts
- graphene oxide
- carboxylic acid
- composite material
- acid series
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention discloses a kind of surface of graphene oxide molecular imprinting composite material for tracking poly carboxylic acid series water reducer, which is made according to following mass parts：100 ~ 120 parts of graphene oxide layer dispersion liquids, 10 ~ 30 parts of poly carboxylic acid series water reducers, 0.5 ~ 0.8 part of acrylamide, 2 ~ 4 parts of ethyl orthosilicates, 1.2 ~ 1.5 parts of azo-bis-iso-dimethyls；The invention also discloses a kind of preparation methods for tracking the surface of graphene oxide molecular imprinting composite material of poly carboxylic acid series water reducer, graphene oxide low problem of dispersibility in cement-base composite material is improved through the invention, enhance GO nanoscale twins shape and surface-active point to the template action of hydrated reaction of cement and its product, growth of the flower shape GO aquations crystal in the hole, soft place of cement-based material is promoted, GO mutually penetrating in cement-based material is improved and connects into the trend of reticular structure to different directions.
Description
Technical field
The invention belongs to imprinted material technical field more particularly to a kind of oxidation stones for tracking poly carboxylic acid series water reducer
Black alkene surface molecule print composite material and preparation method.
Technical background
Cement-base composite material is the maximum construction material of currently used amount, presently, there are greatest problem be to use
Crack and leakage are easy tod produce in journey, cause its service life short, the high brittleness for the mainly cement-base composite material of tracing it to its cause
And hydrolysis product of cement structure can not regulate and control caused by caused by crack, hole, find a kind of passes through and change hydrated cementitious production
The structure of object is come the hot spot that the mechanical property that improves cement-base composite material is current research.
Graphene oxide is a kind of derivative of graphene, and surface carries multiple active groups, toughness with superelevation and
Big specific surface area.Mould can be generated to hydrated reaction of cement and its product by adding graphene oxide into cement-base composite material
Plate effect can regulate and control hydrolysis product of cement and form regular orderly structure, the formation of cement-based material inside is promoted mutually to penetrate,
The reticular structure of intertexture improves the pore structure of Behavior of Hardened Cement Paste, enhances its compactness, and then enhance the mechanical property of cement-base composite material
(Wang Qin, Wang Jian, Lv Chunxiang, Liu Baiwei, Zhang Kun, Li Chongzhi, graphene oxide are microcosmic to cement-base composite material for energy
Influence [J] novel charcoal materials of structure and mechanical property, 2015,30 (4): 249-356).This method is existing to aoxidize stone
The not high problem of dispersibility of the black alkene in cement-base composite material, hinders graphene oxide answering in cement-based material
With.
Molecular imprinting technology is a kind of polymer technology of preparing to target substance with specific identification ability.The technology is first
First template molecule and function monomer are chemically combined, then under the action of initiator, make it that polymerisation occur with crosslinking agent,
Target molecule imprinted polymer is obtained after eluted template molecule.Molecularly imprinted polymer selects target substance with high stable
Property, it can quickly identify and isolate target substance.
Under this technical background, using the anti-thinking tracked, using graphene oxide as substrate, in cement-base composite material
The poly carboxylic acid series water reducer of middle good dispersion is template molecule, and polymerisation occurs with function monomer, initiator, crosslinking agent, washes
It is de- to obtain a kind of surface of graphene oxide molecular imprinting composite material for tracking poly carboxylic acid series water reducer.First by polycarboxylic-acid
Water-reducing agent is added in cement-base composite material and stirs evenly, and the surface of graphene oxide molecular imprinting composite material is then added,
The polycarboxylic-acid being dispersed in cement-base composite material is found to the special absorption identity of template molecule using imprinted polymer
Graphene oxide is uniformly dispersed in cement-base composite material by water-reducing agent with this, to improve graphene oxide to cement
Hydrated product and the regulating and controlling effect of microstructure in based composites improve the mechanical property of cement-base composite material, reduce and split
Seam and hole, extend the service life of cement-base composite material.
Invention content
In view of this, the main purpose of the present invention is to provide a kind of graphite oxides for tracking poly carboxylic acid series water reducer
Alkene surface molecule print composite material and preparation method.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：
It is multiple that the embodiment of the present invention provides a kind of surface of graphene oxide molecular engram for tracking poly carboxylic acid series water reducer
Condensation material, the composite material are made according to following mass parts：100 ~ 120 parts of graphene oxide layer dispersion liquids, 10 ~ 30 parts of poly- carboxylics
Sour based water reducer, 0.5 ~ 0.8 part of acrylamide, 2 ~ 4 parts of ethyl orthosilicates, 1.2 ~ 1.5 parts of azo-bis-iso-dimethyls.
In said program, the formic acid and alcohol mixed solution are that 50 ~ 60 parts of formic acid and 20 ~ 30 parts of ethyl alcohol are mixed
Uniformly gained.
In said program, the solid content of graphite oxide is 1.5% ~ 5% in the stannic oxide/graphene nano lamella dispersion liquid, ruler
Very little is 30 ~ 100 nm.
In said program, the molecular weight of the poly carboxylic acid series water reducer is 73000 ~ 74000, when in cement-base composite material
In volume be 0.2% when, water-reducing rate is up to 31%.
In said program, the azo-bis-iso-dimethyl is a kind of not cyano-containing, and initiation activity is moderate, manageable
Azo-initiator.
The embodiment of the present invention also provides a kind of surface of graphene oxide molecular engram for tracking poly carboxylic acid series water reducer
The preparation method of composite material, the preparation method are：It will be in 10 ~ 30 parts of poly carboxylic acid series water reducers and 40 ~ 60 parts of absolute ethyl alcohols
Ultrasound 30min is mixed, three-necked flask is then mixed to join with 0.5 ~ 0.8 part of function monomer acrylamide, controls temperature in bottle
It is 55 DEG C, stirs prepolymerization 3h, template molecule is made to be sufficiently mixed with function monomer, 100 ~ 120 parts of graphene oxides is then added
Lamella dispersion liquid, 2 ~ 4 parts of crosslinking agent ethyl orthosilicates and 1.2 ~ 1.5 parts of initiator azo-bis-iso-dimethyls, are passed through nitrogen
After 25min, be warming up to 80 DEG C, be stirred to react 18h, after mixed liquor is placed in Soxhlet extractor, with 70 ~ 90 parts of formic acid
15h is extracted with alcohol mixed solution, is then washed with deionized to neutrality, 70 DEG C of vacuum drying chamber drying 6h is placed in, obtains
Surface of graphene oxide molecular imprinting composite material for tracking poly carboxylic acid series water reducer.
Compared with prior art, beneficial effects of the present invention：
The present invention is using graphene oxide as substrate, and using poly carboxylic acid series water reducer as template molecule, function monomer propylene is added
Amide, crosslinking agent ethyl orthosilicate and initiator azo-bis-iso-dimethyl prepare surface of graphene oxide molecular engram
Composite material, the low problem of dispersibility that present invention improves graphene oxides in cement-base composite material, enhances GO nanometers
Shape and the surface-active point of lamella promote flower shape GO aquation crystal to the template action of hydrated reaction of cement and its product
In the growth of the hole, soft place of cement-based material, GO mutually penetrating in cement-based material is improved and to different directions
Connect into the trend of reticular structure；Compared with general graphene oxide cement additive, it is multiple significantly to improve cement base
The compression strength and flexural strength of condensation material have active influence to the cracking resistance seam and durability that solve concrete construction.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
It is multiple that the embodiment of the present invention provides a kind of surface of graphene oxide molecular engram for tracking poly carboxylic acid series water reducer
Condensation material, the composite material are made according to following mass parts：100 ~ 120 parts of graphene oxide layer dispersion liquids, 10 ~ 30 parts of poly- carboxylics
Sour based water reducer, 0.5 ~ 0.8 part of acrylamide, 2 ~ 4 parts of ethyl orthosilicates, 1.2 ~ 1.5 parts of azo-bis-iso-dimethyls.
The formic acid and alcohol mixed solution are that gained is mixed evenly in 50 ~ 60 parts of formic acid and 20 ~ 30 parts of ethyl alcohol.
The solid content of graphite oxide is 1.5% ~ 5% in the stannic oxide/graphene nano lamella dispersion liquid, and size is 30 ~ 100
nm。
The molecular weight of the poly carboxylic acid series water reducer is 73000 ~ 74000, when the volume in cement-base composite material is
When 0.2%, water-reducing rate is up to 31%.
The azo-bis-iso-dimethyl is a kind of not cyano-containing, causes active moderate, manageable azo initiation
Agent.
The embodiment of the present invention also provides a kind of surface of graphene oxide molecular engram for tracking poly carboxylic acid series water reducer
The preparation method of composite material, the preparation method are：It will be in 10 ~ 30 parts of poly carboxylic acid series water reducers and 40 ~ 60 parts of absolute ethyl alcohols
Ultrasound 30min is mixed, three-necked flask is then mixed to join with 0.5 ~ 0.8 part of function monomer acrylamide, controls temperature in bottle
It is 55 DEG C, stirs prepolymerization 3h, template molecule is made to be sufficiently mixed with function monomer, 100 ~ 120 parts of graphene oxides is then added
Lamella dispersion liquid, 2 ~ 4 parts of crosslinking agent ethyl orthosilicates and 1.2 ~ 1.5 parts of initiator azo-bis-iso-dimethyls, are passed through nitrogen
After 25min, be warming up to 80 DEG C, be stirred to react 18h, after mixed liquor is placed in Soxhlet extractor, with 70 ~ 90 parts of formic acid
15h is extracted with alcohol mixed solution, is then washed with deionized to neutrality, 70 DEG C of vacuum drying chamber drying 6h is placed in, obtains
Surface of graphene oxide molecular imprinting composite material for tracking poly carboxylic acid series water reducer.
Embodiment one：
Step 1：The preparation of graphene oxide layer dispersion liquid
2 parts of graphite powders, 50 parts of concentrated sulfuric acids are sequentially added in three-necked flask.Control system temperature is 3 DEG C, in 1h slowly
2 parts of sodium nitrate are added, 8 parts of potassium permanganate, the reaction was continued 2 hours.35 DEG C are warming up to, after medium temperature reacts 6h, is slowly added dropwise 100 parts
30min is added dropwise in deionized water.It is warming up to 85 DEG C again, after pyroreaction 40min, 150 parts of deionized waters is slowly added dropwise, be added dropwise
30min, when system temperature is reduced to 50 DEG C, the hydrogen peroxide that 1.8 parts of mass fractions are 30%, which is added, makes solution turned yellow, uses deionization
It is washed to solution to be in neutrality, by mixed liquor ultrasonic disperse 40min, obtains graphene oxide layer dispersion liquid.
Step 2：Track the preparation of the surface of graphene oxide molecular imprinting composite material of poly carboxylic acid series water reducer
10 parts of poly carboxylic acid series water reducers are mixed into ultrasound 30min with 40 parts of absolute ethyl alcohols, then with 0.5 part of function monomer third
Acrylamide is mixed to join three-necked flask, and it is 55 DEG C to control temperature in bottle, stirs prepolymerization 3h, makes template molecule and function monomer
It is sufficiently mixed.Then 100 parts of graphene oxide layer dispersion liquids, 2 parts of ethylene glycol dimethacrylates and 1.2 parts of azos are added
Two isobutyl dimethyl phthalates.After being passed through nitrogen 25min, be warming up to 80 DEG C, be stirred to react 18h, after mixed liquor is placed in Soxhlet
In extractor, 15h is extracted with 70 parts of formic acid and alcohol mixed solution, is then washed with deionized to neutrality, is placed in 70 DEG C very
Empty drying box dries 6h, obtains the surface of graphene oxide molecular imprinting composite material of tracking poly carboxylic acid series water reducer.
Embodiment two：
Step 1：The preparation of graphene oxide layer dispersion liquid
4 parts of graphite powders, 100 parts of concentrated sulfuric acids are sequentially added in three-necked flask.Control system temperature is 4 DEG C, is delayed in 1h
Slowly 4 parts of sodium nitrate are added, 16 parts of potassium permanganate, the reaction was continued 3 hours.35 DEG C are warming up to, after medium temperature reacts 7h, is slowly added dropwise
50min is added dropwise in 180 parts of deionized waters.It is warming up to 85 DEG C again, after pyroreaction 40min, 180 parts of deionized waters is slowly added dropwise, drip
Add 50min, when system temperature is reduced to 60 DEG C, the hydrogen peroxide that 4 parts of mass fractions are 30%, which is added, makes solution turned yellow, uses deionization
It is washed to solution to be in neutrality, by mixed liquor ultrasonic disperse 80min, obtains graphene oxide layer dispersion liquid.
Step 2：Track the preparation of the surface of graphene oxide molecular imprinting composite material of poly carboxylic acid series water reducer
30 parts of poly carboxylic acid series water reducers are mixed into ultrasound 30min with 60 parts of absolute ethyl alcohols, then with 0.8 part of function monomer third
Acrylamide is mixed to join three-necked flask, and it is 55 DEG C to control temperature in bottle, stirs prepolymerization 3h, makes template molecule and function monomer
It is sufficiently mixed.Then 120 parts of graphene oxide layer dispersion liquids, 4 parts of ethylene glycol dimethacrylates and 1.5 parts of azos are added
Two isobutyl dimethyl phthalates.After being passed through nitrogen 25min, be warming up to 80 DEG C, be stirred to react 18h, after mixed liquor is placed in Soxhlet
In extractor, 15h is extracted with 90 parts of formic acid and alcohol mixed solution, is then washed with deionized to neutrality, is placed in 70 DEG C very
Empty drying box dries 6h, obtains the surface of graphene oxide molecular imprinting composite material of tracking poly carboxylic acid series water reducer.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (3)
1. a kind of surface of graphene oxide molecular imprinting composite material for tracking poly carboxylic acid series water reducer, which is characterized in that
The composite material is made according to following mass parts：100 ~ 120 parts of graphene oxide layer dispersion liquids, 10 ~ 30 parts of polycarboxylic-acids subtract
Aqua, 0.5 ~ 0.8 part of acrylamide, 2 ~ 4 parts of ethyl orthosilicates, 1.2 ~ 1.5 parts of azo-bis-iso-dimethyls；The oxidation stone
The solid content of graphite oxide is 1.5% ~ 5% in black alkene nanoscale twins dispersion liquid, and size is 30 ~ 100 nm.
2. the surface of graphene oxide molecular engram composite wood according to claim 1 for tracking poly carboxylic acid series water reducer
Material, it is characterised in that：The molecular weight of the poly carboxylic acid series water reducer is 73000 ~ 74000, when in cement-base composite material
When volume is 0.2%, water-reducing rate is up to 31%.
3. a kind of preparation method for tracking the surface of graphene oxide molecular imprinting composite material of poly carboxylic acid series water reducer,
It is characterized in that, which is：10 ~ 30 parts of poly carboxylic acid series water reducers are mixed into ultrasound with 40 ~ 60 parts of absolute ethyl alcohols
30min is then mixed to join three-necked flask with 0.5 ~ 0.8 part of function monomer acrylamide, and it is 55 DEG C to control temperature in bottle, is stirred
Prepolymerization 3h is mixed, template molecule is made to be sufficiently mixed with function monomer, 100 ~ 120 parts of graphene oxide layer dispersions are then added
Liquid, 2 ~ 4 parts of crosslinking agent ethyl orthosilicates and 1.2 ~ 1.5 parts of initiator azo-bis-iso-dimethyls, after being passed through nitrogen 25min,
Be warming up to 80 DEG C, be stirred to react 18h, after mixed liquor is placed in Soxhlet extractor, it is mixed with 70 ~ 90 parts of formic acid and ethyl alcohol
It closes solution and extracts 15h, be then washed with deionized to neutrality, be placed in 70 DEG C of vacuum drying chamber drying 6h, obtain for tracking
The surface of graphene oxide molecular imprinting composite material of poly carboxylic acid series water reducer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610092458.3A CN105731861B (en) | 2016-02-19 | 2016-02-19 | Surface of graphene oxide molecular imprinting composite material and preparation method thereof for tracking poly carboxylic acid series water reducer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610092458.3A CN105731861B (en) | 2016-02-19 | 2016-02-19 | Surface of graphene oxide molecular imprinting composite material and preparation method thereof for tracking poly carboxylic acid series water reducer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105731861A CN105731861A (en) | 2016-07-06 |
| CN105731861B true CN105731861B (en) | 2018-08-17 |
Family
ID=56245410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610092458.3A Expired - Fee Related CN105731861B (en) | 2016-02-19 | 2016-02-19 | Surface of graphene oxide molecular imprinting composite material and preparation method thereof for tracking poly carboxylic acid series water reducer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105731861B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108911654B (en) * | 2018-08-15 | 2020-09-08 | 陕西科技大学 | Modified graphene oxide concrete crack repairing material and preparation method thereof |
| CN115093182B (en) * | 2022-07-27 | 2023-08-01 | 青岛理工大学 | In-situ organic-inorganic polymerization modified cement-based composite material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604009A (en) * | 2012-03-23 | 2012-07-25 | 济南大学 | Preparation method of molecularly imprinted polymer of magnetic graphene carrier |
| US8951343B2 (en) * | 2012-08-31 | 2015-02-10 | Metna Co. | Ultra high performance concrete reinforced with low-cost graphite nanomaterials and microfibers, and method for production thereof |
| CN103241983B (en) * | 2013-05-22 | 2014-07-16 | 陕西科技大学 | Preparation method of graphene oxide modified polycarboxylic acid type water-reducer |
| CN104086112A (en) * | 2014-06-25 | 2014-10-08 | 江苏奥莱特新材料有限公司 | Multifunctional enhancement-type concrete admixture and preparation method thereof |
| CN104876204B (en) * | 2015-05-21 | 2017-03-01 | 东南大学 | A kind of method of modifying of graphene oxide |
-
2016
- 2016-02-19 CN CN201610092458.3A patent/CN105731861B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105731861A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101775107B (en) | Preparation method of concrete polycarboxylate water-reducer at normal temperature | |
| CN101619366B (en) | Preparation method of amphoteric vinyl polymer/ZnO nanocomposite tanning agent | |
| CN105731861B (en) | Surface of graphene oxide molecular imprinting composite material and preparation method thereof for tracking poly carboxylic acid series water reducer | |
| CN101480604B (en) | Method for preparing silver/carbon nano composite body | |
| CN104894302B (en) | Graphene oxide/ferrum nano-composite tanning agent and preparation method thereof | |
| CN104558323A (en) | High-water-solubility nanometer hexagonal boron nitride and preparation method of polymer composite hydrogel of high-water-solubility nanometer hexagonal boron nitride | |
| CN104934237B (en) | A kind of preparation method of nitrating porous charcoal/graphene two dimension combination electrode material | |
| CN106145794A (en) | A kind of uvioresistant environment-friendly concrete | |
| CN108084363A (en) | A kind of preparation method of reinforcing type polycarboxylic acid water-reducing agent | |
| CN111675453B (en) | Lake sediment curing agent | |
| CN104743550B (en) | Three-dimensional macroscale graphene and preparation method thereof | |
| CN109971047B (en) | Natural rubber-white carbon black composite material and preparation method and application thereof | |
| CN104892856B (en) | A kind of preparation method of polycarboxylate water-reducer | |
| CN106116580B (en) | A kind of flexibility carbon film and preparation method thereof | |
| CN108948259B (en) | Modified graphene oxide few-lamellar water-phase uniform dispersion liquid for cement-based composite material, and preparation method and application thereof | |
| CN108163845A (en) | A kind of preparation method of porous graphene material | |
| CN107827104A (en) | A kind of graphene oxide microballoon, the preparation method of graphene microballoon | |
| CN105779668B (en) | Zirconium tanning agent/stannic oxide/graphene nano composite tanning agent and preparation method thereof | |
| CN109265624B (en) | Preparation method of concrete reinforcing agent | |
| CN101693619B (en) | Method for preparing high-imitation stone sculpture by utilizing stone powder | |
| CN106984289B (en) | A kind of preparation method of porous ceramic surface perfluoro caprylic acid molecular imprinting adsorbing agent | |
| CN103467915A (en) | Preparation method of functional carbon nanotube/epoxy resin composite material | |
| CN109467408A (en) | Oxide modifying full information surface silica gel mould cinder infuses solidification forming method | |
| CN105175686A (en) | Preparation method of epoxy resin modified by ultra-dispersed nano calcium carbonate | |
| CN104450995B (en) | SiO 2aerogel/vinyl polymer compound high absorption chrome tanning adjuvant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Lv Shenghua Inventor after: Hu Haoyan Inventor after: Jia Chunmao Inventor after: He Yaya Inventor before: Lv Shenghua Inventor before: Jia Chunmao Inventor before: He Yaya |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190515 Address after: 550018 No.2 Building of Paddy Field Town, Paddy Field Village, Wudang District, Guiyang City, Guizhou Province Patentee after: Guizhou Kezhu Creative Building Technology Co., Ltd. Address before: 710021 Shaanxi City, Xi'an City, Weiyang City Patentee before: Shaanxi University of Science and Technology |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180817 Termination date: 20200219 |